US4146438A - Sintered electrodes with electrocatalytic coating - Google Patents

Sintered electrodes with electrocatalytic coating Download PDF

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Publication number
US4146438A
US4146438A US05/774,101 US77410177A US4146438A US 4146438 A US4146438 A US 4146438A US 77410177 A US77410177 A US 77410177A US 4146438 A US4146438 A US 4146438A
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United States
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electrode
sintered
oxides
group
electrocatalyst
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US05/774,101
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Vittorio De Nora
Placido M. Spaziante
Antonio Nidola
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ELECTRODE Corp A DE CORP
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Diamond Shamrock Technologies SA
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
    • C25C3/12—Anodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof

Definitions

  • Electrodes for anodic and cathodic reactions in electrolysis cells have recently become of general use in the electrochemical industry replacing the consumable electrodes of carbon, graphite and lead alloys. They are particularly useful in flowing mercury cathode cells and in diaphragm cells for the production of chlorine and caustic, in metal electrowinning cells wherein pure metal is recovered from aqueous chloride or sulfate solution as well as for the cathodic protection of ships' hulls and other metal structures.
  • British Pat. No. 1,295,117 discloses anodes for molten cryolite baths consisting of a sintered ceramic oxide material consisting substantially of SnO 2 with minor amounts of other metal oxides, namely, oxides of Fe, Sb, Cr, Nb, Zn, W, Zr, Ta in concentration of up to 20%. While electrically conducting sintered SnO 2 with minor additions of other metal oxides, such as oxides of Sb, Bi, Cu, U, Zn, Ta, As, etc., has been used for a long time as a durable electrode material in alternating current glass smelting furnaces (see U.S. Pat. Nos.
  • Coatings of particulate spinels and/or perovskites have been found, however, to be mechanically weak as the bonding between the particulate ceramic coating and the metal or carbon substrate is inherently weak, because the crystal structure of the spinels and of the perovskites are not isomorphous with the oxides of the metal support and various binding agents such as oxides, carbides, nitrides and borides have been tried with little or no improvement.
  • the substrate material is rapidly attacked due to the inevitable pores through the spinel oxide coating and the coating is quickly spalled off the corroding substrate.
  • spinels and perovskites are not chemically or electrochemically stable in molten halide salt electrolytes and show an appreciable wear rate due to halide ion attack and to the reducing action of dispersed metal.
  • An electrode material to be used successfully in severely corrosive conditions such as in the electrolysis of molten halide salts and particularly of molten fluoride salts should primarily be chemically and electrochemically stable at the operating conditions. It should also be catalytic with respect to the anodic evolution of oxygen and/or halides, so that the anode overpotential is lowest for high overall efficiency of the electrolysis process.
  • the electrode should also have the thermal stability at operating temperatures of, i.e., about 200° to 1100° C., good electrical conductivity and be sufficiently resistant to accidental contact with the molten metal cathode. Excluding coated metal electrodes, since hardly any metal substrate could resist the extremely corrosive conditions found in molten fluoride salt electrolysis, we have systematically tested the performances of a very large number of sintered substantially ceramic electrodes of different compositions.
  • the novel electrodes of the invention are comprised of a self-sustaining matrix of sintered powders of an oxycompound of at least one metal selected from the group consisting of titanium, tantalum, zirconium, vanadium, niobium, hafnium, aluminum, silicon, tin, chromium, molybdenum, tungsten, lead, manganese, beryllium, iron, cobalt, nickel, platinum, palladium, osmium, iridium, rhenium, technetium, rhodium, ruthenium, gold, silver, cadmium, copper, scandium and metals of the lanthanide and actinide series and at least one electroconductive agent, the said electrodes being provided over at least a portion of their surface with at least one electrocatalyst.
  • Preferred metals of lanthanide and actinide series are lanthanum, terbium, erbium, thorium and ytterbium.
  • the preferred electrocatalysts are selected from the group of metals consisting of ruthenium, rhodium, palladium, iridium, platinum, iron, cobalt, nickel, copper and silver and mixtures thereof and oxides of metals of the group consisting of manganese, iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum, silver, arsenic, antimony, lead and bismuth and mixtures thereof.
  • additives are added in powder form and mixed with the powdered metal oxide in percentages which may range from 40 to 1% calculated in terms of weight of the metal content.
  • organic and/or inorganic compounds may be added to the powder mixture to improve on the bonding of the particles during both the moulding and sintering processes.
  • the conductivity of the sintered electrodes of the invention is comparable with that of graphite.
  • the matrix has acceptable work-ability in the forming and sintering operation and in use forms a thin layer of oxyhalides on its surface under anodic conditions.
  • the metal oxycompounds free formation energy is more negative than the oxide free formation energy of the corresponding halide-phase fused salt electrolyte, so that these sintered anodes have a high degree of chemically stability.
  • the molded electrodes are then subjected to a drying process and heated at a temperature at which the desired bonding can take place, usually between 800° to 1800° C. for a period of between 1 to 30 hours, normally followed by slow cooling to room temperature.
  • the heat treatment is preferably carried out in an inert atmosphere or one that is slightly reducing, for example in H 2 + N 2 (80%), when the powdered mixture is composed essentially of oxymetal compound with a minor portion of other metal oxides or metals.
  • the powdered mixture contains also metallic powders
  • the metallic particles remaining inside the body of the sintered material improve the electrical conductivity properties of the electrode.
  • the forming process may be followed by the sintering process at a high temperature as mentioned above or the forming process and the sintering process may be simultaneous, that is, pressure and temperature may be applied simultaneously to the powder mixture, for example by means of electrically-heated molds.
  • Lead-in connectors may be fused into the ceramic electrodes during the molding and sintering process or attached to the electrodes after sintering or molding. Other methods of shaping, compressing and sintering the powder mixture may of course be used.
  • Poisons for the suppression of unwanted anodic reactions may be used, such as, for example, to suppress oxygen evolution from chloride electrolytes.
  • Poisons which present a high oxygen overpotential should be used and suitable materials are the oxides of arsenic, antimony and bismuth. These oxides which are used in small percentages may be applied together with the electrocatalyst oxides in percentage of 1 to 10% of the electrocatalyst calculated in terms of the respective metals weight.
  • One preferred method to apply a layer is by plasma-jet technique whereby powders of the selected materials are sprayed and adhere to the surface of the sintered body with a flame under controlled atmosphere.
  • the selected powdered material may be added during the forming process to the powder mixture and thence be sintered together whereby the cathodic surface of the bipolar electrode is provided with a layer of the selected cathodic material.
  • the electrodes may be used effectively for the electrolysis of many electrolytes. They are especially advantageous when used as anodes in electrolytic cells used for electrolyzing molten salt electrolytes such as molten cryolite baths, molten halides of aluminum, magnesium, sodium, potassium, calcium, lithium and other metals.
  • molten salt electrolytes such as molten cryolite baths
  • molten halides of aluminum, magnesium, sodium, potassium, calcium, lithium and other metals molten halides of aluminum, magnesium, sodium, potassium, calcium, lithium and other metals.
  • aluminum halides may be electrolyzed according to the Hall process or processes disclosed in U.S. Pat. Nos. 3,464,900, 3,518,712 or 3,755,099 (the disclosure of which is incorporated herein by reference) using the electrodes herein described as anodes.
  • the temperature of electrolysis is high enough to melt and maintain the salts of the metal to be recovered in a molten state and the metal is deposited in the molten state and usually collected as a molten cathode with molten metal being withdrawn from the molten cathode.
  • the composition of the cathode portion of the electrodes must be such that it will not be reduced by the cathodic reaction or attacked by the metal being deposited at the cathodes, particularly when the electrode composition is an oxycompound. For this reason, it is desirable to have the composition of the cathode side of the bipolar electrode inert to the cathodic reaction and the reducing action of the molten metal.
  • the electrodes may also be used as anodes and/or as cathodes in electrochemical processes such as: the electrolysis of aqueous chloride solutions for the production of chlorine, caustic, hydrogen, hypochlorite, chlorates and perchlorates; the electrowinning of metals from aqueous sulfate or chloride solutions for the production of copper, zinc, nickel, cobalt and other metals; the electrolysis of molten metal salt electrolytes typically containing halides, oxides, carbonates or hydrates for the production of aluminum, beryllium, calcium, lithium, sodium, magnesium, potassium, barium, strontium, cesium and other metals and the electrolysis of bromides, sulfides, sulfuric acid, hydrochloric acid and hydrofluoric acid.
  • the electrodes are useful for all electrolytic processes.
  • the novel electrolysis method of the invention comprises electrolyzing an electrolyte between an anode and a cathode, the improvement residing in the anode being comprised of a self-sustaining matrix of sintered powders of an oxycompound of at least one metal selected from the group consisting of titanium, tantalum, zirconium, vanadium, niobium, hafnium, aluminum, silicon, tin, chromium, molybdenum, tungsten, lead, manganese, beryllium, iron, cobalt, nickel, platinum, palladium, osmium, iridium, rhenium, technetium, rhodium, ruthenium, gold, silver, cadmium, copper, zinc, germanium, arsenic, antimony, bismuth, boron, scandium and metals of the lanthanide and actinide series and at least one electroconductive agent, the said electrodes being provided over at least a portion of their surface with at least one electrocat
  • the preferred anodes are those wherein the major portion of the self-sustaining body is tin dioxide alone or with up to 20% by weight of cobalt oxide provided with a coating of cobalt oxide which give electrodes of improved mechanical properties and electrocatalytic properties for chlorine evolution.
  • Other preferred additives are Y 2 O 3 , TiO 2 and Ta 2 O 5 .
  • the electrocatalyst coating may be protected against wear by the simultaneous or subsequent application of a protective agent such as a valve metal oxide like TiO 2 and Ta 2 O 5 or SiO 2 mixed oxides such as AgRe 2 O 3 , TiCo 2 O 4 and Ag x WO 3 .
  • a protective agent such as a valve metal oxide like TiO 2 and Ta 2 O 5 or SiO 2 mixed oxides such as AgRe 2 O 3 , TiCo 2 O 4 and Ag x WO 3 .
  • the electrode samples were then used as anodes in a test cell for the electrolysis of aluminum chloride at 750° C. and an anodic current density of 1000 A/m 2 .
  • the cell voltage was 5 volts and the electrolyte was a 5-1-1 mixture by weight of aluminum chloride, sodium chloride and potassium chloride.
  • the anodic potential was determined initially and after 500 hours of operation and the weight loss of the electrode was determined after 500 hours.
  • a standard graphite electrode was also used under the same conditions and the results are reported in Table I.
  • Table II shows that the electrodes of the invention have a low wear rate and a low anode potential even after 300 hours of operation.
  • Disc-shaped electrodes with a diameter of 10 mm and a thickness of 5 mm were prepared from powders having a mesh number of 100 to 250.
  • the powders were press-moulded at a pressure of 1000 Kg/cm 2 and were then sintered in an induction furnace under the conditions reported in Table III which also shows the compositions of the powders.
  • the sintering was conducted in a furnace through which the indicated gas was circulated or maintained at atmospheric pressure.
  • the indicated gas was circulated or maintained at atmospheric pressure.
  • the external surfaces, and perhaps some of the external pores were exposed to an oxidizing atmosphere at the temperature indicated and the exposed metal in the surfaces were oxidized to form the electrocatalyst.
  • the electrode samples were used as anodes in a test cell for the electrolysis of aluminum chloride at 750° C. and an anodic current density of 1000 A/m 2 .
  • the cell voltage was 5 volts and the electrolyte was a 5-1-1 mixture of aluminum chloride, sodium chloride and potassium chloride.
  • the anodic potential was determined initially and after 500 hours of operation, and the weight loss of the electrode was determined after 500 hours.
  • a reference graphite electrode was also used under the same conditions and the results are reported in Table IV.
  • Electrode 8 which did not contain any additive electroconductive metal, had a substantially higher over-potential for chlorine evolution and the reference graphite electrode had an over-potential above the values for electrodes 1 to 7 and a high wear rate.
  • the reference graphite anode needed substantial adjustments during the electrolysis and an early replacement. The average efficiency during the test was 97%. All of the samples 1 to 7, inclusive, were less brittle than Sample No. 8.
  • the data in Table V shows that the electrical conductivity of the sintered ceramic electrodes at high temperatures of 1000° C. is 5 to 10 times higher than the electrical conductivity at 25° C.
  • the addition of oxides having conductivity equivalent to metals to the substantially non-conductive ceramic oxides of the matrix increases the conductivity of the electrodes by a magnitude of 10 2 .
  • the addition of a metal stable to molten salts such as yttrium or molybdenum, etc. to the ceramic electrodes of the invention increases the electrical conductivity of the electrodes by 2 to 5 times.
  • the test sample electrodes operated successfully as anodes in the cryolite melt and the observed wear rates appear to be quite acceptable for the electrolytic production of aluminum from molten cryolite. All the tested electrodes showed a low wear rate during 2000 hours of operation. In general, the wear rate of the electrodes containing thermal stabilizers such as oxycompounds of metals of Group III of the Periodic Table is about 10 times less than the electrodes without thermal stabilizers.
  • Electrodes Nos. 4 and 5 described in Table V were used as anodes for the electrolysis of a molten aluminum chloride electrolyte in the test cell described in Example 5.
  • the electrolysis conditions were the following:
  • Electrode samples Nos. 10, 11 and 13 of Example 1 were used alternatively as anode and as cathode in the electrolysis of synthetic sea-water in a test cell in which the electrolyte was pumped through the electrodic gap of 3 mm at a speed of 3 cm/sec.
  • the current density was maintained at 1500 A/m 2 and the spent electrolyte contained 0.8 to 2.4 of sodium hypochlorate with a faraday efficiency of more than 88%.
  • the weight loss of the electrodes after 200 hours of operation was negligible.
  • Electrode samples Nos. 12 and 14 of Example 1 were used as anodes in the electrolysis of an aqueous acidic cupric sulfate solution in a cell with a titanium cathode blank.
  • the electrolyte contained 150 to 200 gpl of sulfuric acid and 40 gpl of cupric sulfate as metallic copper and the anode current density was 300 A/cm 2 .
  • the electrolyte temperature was 60° to 80° C. and an average of 6 mm of copper were deposited on the flat cathode at a faraday efficiency ranging from 92 to 98%.
  • the quality of the metal deposit was good and free of dendrites and the anode overvoltage was very low, ranging from 1.81 to 1.95 V(NHE).
  • Electrocatalysts which may be used in the electrolysis of molten halide salts for halide ion discharge are RuO 2 and oxides such as As 2 O 3 , Sn 2 O 3 and Bi 2 O 3 may be added in percentages up to 10% by weight of free metal based upon the total metal content to rise the oxygen overpotential without affecting the halide ion discharge potential.
  • the catalyst may be those listed in Example 5 or Rh 2 O 3 , PbO 2 and IrO 2 .TiO 2 .
  • the components of the anodes given in the Examples are calculated in percent by weight of free metal based upon the total metal content of the anode composition.
  • the electrolyte may contain other salts than those used in the Examples such as alkali metal chloride or fluoride as well as the salt of the metal undergoing electrolysis.
  • the metal halides are effective to reduce the melting point of the salt undergoing electrolysis thus permitting use of lower temperatures while maintaining the salt bath in molten or melted state.
  • Electrodes may be used in place of graphite anodes in standard aluminum electrowinning cells with either aluminum ore feed into a cryolite bath or with aluminum chloride feed into a predominately aluminum chloride bath.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
US05/774,101 1976-03-31 1977-03-07 Sintered electrodes with electrocatalytic coating Expired - Lifetime US4146438A (en)

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